ABSTRACT
Recently, transition metal phosphides (TMPs) have been widely explored for the hydrogen evolution reaction (HER) due to their advantaged activity. Nevertheless, the OER performance of TMPs in an alkaline medium is still unsatisfactory. Therefore, interfacial engineering of TMPs to enhance the OER performance is highly desirable. Herein, a Co(OH)2 nanosheet coupled with a CoP sphere supported on nickel foam (NF) is developed by a simple two-step electrodeposition. The large surface area derived from stacked nanosheets and the electronic regulation induced by heterostructure can significantly enhance charge/mass transfer and expose more active sites, thus accelerating the kinetics of the reaction. In addition, the strong electronic interaction between CoP and Co(OH)2 is conducive to the generation of a high valence cobalt center; thus, the electrocatalytic performances toward HER and OER are remarkably improved. Impressively, the optimized CoP/Co(OH)2@NF heterostructure obtains an excellent HER and OER performance with low overpotentials of 76 and 266 mV at 10 mA cm-2, respectively, superior to the commercial Pt/C and RuO2. Moreover, the optimized CoP/Co(OH)2@NF can afford the lowest cell voltage of 1.58 V to achieve 10 mA cm-2 for alkaline overall water splitting and shows outstanding long-term stability.
ABSTRACT
Trilobatin is a flavonoid that has wide application prospects due to its various pharmacological effects, such as anti-inflammation and anti-oxidation. In this work, a novel electrochemical sensor based on gold nanobipyramids (AuNBs) and L-cysteine (L-cys) was constructed for the sensitive and selective determination of trilobatin. The AuNBs, which were prepared by a seed-mediated growth method, had large specific surface areas and excellent electrical conductivity. A layer of L-cys film, which provided more active sites through the amino and hydroxyl groups, was modified on the surface of the AuNBs by electropolymerization. Significantly, the Au-S bond between the L-cys film and AuNBs could improve the stability of the sensor and it exhibited satisfactory electrocatalytic oxidation activity for trilobatin. Under optimized conditions, the sensor based on poly-L-cys/AuNBs/GCE was used to determine trilobatin by differential pulse voltammetry (DPV). Two wide linear ranges between the current peak and the concentration of trilobatin were obtained in the range from 5 to 100 µM and 100 to 1000 µM, and the low detection limit (LOD) was up to 2.55 µM (S/N = 3). The sensor demonstrated desirable reproducibility, stability, and selectivity and was applied to detect real trilobatin samples extracted from Lithocarpus polystachyus Rehd.'s leaves, showing recoveries of 98.36%-104.96%, with satisfactory results.
Subject(s)
Cysteine , Gold , Gold/chemistry , Reproducibility of Results , Oxidation-Reduction , Electrochemical Techniques , ElectrodesABSTRACT
The oxygen reduction reaction and oxygen evolution reaction (ORR-OER) in DMSO were investigated by cyclic voltammetry and potentiostatic methods. A quartz crystal microbalance (QCM) was used to detect which products are formed during reduction and to evaluate the reversibility of the reactions. The studied parameters include the scan rate and the applied cathodic potential. We confirm by the QCM that LiO2 is soluble: this conclusion comes from the time delay we observed between the deposition of the expected mass (based on Faraday's law) and the measured mass. Ambiguity in reported literature values for the slope of the deposited mass per electron M/z is due to the negligence in considering this time delay. The average M/z value versus cathodic charge indicates that soluble LiO2 is the first product of the ORR which reacts further to form Li2O2, either via a disproportionation reaction or via further electrochemical reduction of LiO2. For strong negative potentials and thus large depths of discharge, Li2O is the main discharge product. The reaction pathways hence strongly depend on the experimental conditions applied; especially the reduction potential. The redox mediator tetrathiafulvalene (TTF) was investigated and its influence on reversibility was confirmed by cycling at moderate depths of discharge, where Li2O2 is the main discharge product.
ABSTRACT
The electrodeposition of germanium at elevated temperatures up to 180 °C and pressures was studied from the ionic liquids 1-butyl-1-methylpyrrolidinium dicyanamide and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide containing [GeCl4(BuIm)2] (where BuIm = 1-butylimidazole) or GeCl4. Cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), rotating ring-disk electrode (RRDE), scanning electron microscope (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), electron backscatter diffraction (EBSD) and Auger electron spectroscopy (AES) were used to investigate the electrochemical behavior and the properties of the electrodeposited germanium. Electrodeposition at elevated temperatures leads to higher deposition rates due to: (1) increase in the diffusion rate of the electroactive germanium compounds; (2) faster electrochemical kinetics in the electrolyte; and (3) higher electrical conductivity of the electrodeposited germanium film. Moreover, the morphology of the germanium film is also of a better quality at higher electrodeposition temperatures due to an increase in adatom mobility.
ABSTRACT
The title compound, C4H8O4Te, crystallized from a solution of Te(4+) in ethyl-ene glycol. The Te(IV) atom is in a distorted seesaw coordination defined by four O atoms from two different ethyl-eneglycate ligands. The C atoms of the ethyl-eneglycate ligands are disorderd over two positions, with population parameters of 50.3â (6) and 49.7â (6)% indicating a statistical distribution. Due to the possibility to transform the primitive monoclinic unit cell into a metrically ortho-rhom-bic C unit cell, the data are twinned and were refined with the twin law -100/0-10/101 with the relative scale factor refining to 1.82â (4)% for the minor component.
ABSTRACT
The electrodeposition of germanium from the ionic liquid 1-butyl-1-methylpyrrolidinium dicyanamide ([BMP][DCA]) and a mixture of [BMP][DCA] and 1-butyl-1-methylpyrrolidinium chloride ([BMP]Cl) was studied using cyclic voltammetry and using an electrochemical quartz crystal microbalance (EQCM). [GeCl4(BuIm)2] (BuIm = N-butylimidazole) was used as germanium source as it has a solubility of 0.47 M, up to 13 times the solubility of GeCl4 in [BMP][DCA]. Cyclic voltammograms show an irreversible electrochemical behavior and two reduction waves were observed. The wave at the more positive potential was assigned to the reduction of Ge(4+) to Ge(2+). The wave at the more negative potential was attributed to the formation of Ge(0). The diffusion coefficient of Ge(4+) in [BMP][DCA] containing 0.1 M [GeCl4(BuIm)2] is 1.1 × 10(-12) m(2) s(-1), and the exchange current density is 2 × 10(-4) A m(-2) at 50 °C. Polymerization of dicyanamide anions took place at the anode in the solution of [BMP][DCA]. The polymerization reaction could be avoided by using an equimolar [BMP]Cl-[BMP][DCA] mixture as electrolyte. Smooth, porous germanium films were electrodeposited on both copper and silicon substrates.
Subject(s)
Electroplating , Germanium/chemistry , Ionic Liquids/chemistry , Nitriles/chemistry , Organometallic Compounds/chemistry , Pyrrolidines/chemistryABSTRACT
In a spectroholographic storage system the defocusing method is often used to obtain spectrum uniformity and improve the quality of the recorded information. However, defocusing introduces vignette and stronger interpixel cross talk in the marginal field of view. We report a method that defocuses the aperture and medium together. Based on the pixel spread function, two inequalities are introduced to estimate the upper and lower bounds of the energy received at the CCD. We balance the spectrum uniformity with interpixel cross talk and vignette and then allow the designer to select optimal structure values of the defocusing spectroholographic storage system, i.e., the defocusing value, aperture size, and fill factors for the spatial light modulator and CCD.
ABSTRACT
In spectroholographic storage systems the defocusing method is often used for spectrum uniformity and quality improvement of recorded information. The same purpose is served by the fractional Fourier transform (FRFT) storage system. To simplify the numerical analysis, we derive the expressions of the Fraunhofer spectrum and the reconstructed image at the detected plane (CCD) for both cases instead of using the Fresnel spectrum and the FRFT spectrum. The recording aperture, spectrum uniformity, and reconstructed information of both systems are investigated. A numerical comparison is also presented.
ABSTRACT
An exposure-schedule theory of uniform diffraction efficiency for a Dynamic-Static speckle multiplexing (DSSM) volume holographic storage system is proposed. The overlap-factor (? overlap) is introduced into the system to compensate for the erasure effect of the static speckle multiplexing scheme. The exposure-schedule which is an inverse recursion formula is determined. Experimental results are obtained in a LiNbO(3):Fe crystal and 400 holograms with uniform diffraction efficiency are achieved by the use of the new exposure-schedule.
ABSTRACT
By use of speckle modulation on the object beam of a volume holographic optical correlation system, we show that the sidelobes of the correlation patterns along the vertical direction, as well as those along the horizontal direction, are well suppressed. A theoretical explanation and experimental results are presented and discussed.
ABSTRACT
A nonuniform photovoltaic field is created in Fe:LiNbO3 during hologram recording exposures. Experimental results and analysis show the degradation of the volume holograms in the presence of the photovoltaic field. A sodium chloride solution is used to short-circuit the crystal to improve the stored-image quality. Experimental results to demonstrate the effectiveness of the proposed method are presented.
